US7208642B2 - Process for preparation of formate esters or methanol and catalyst therefor - Google Patents

Process for preparation of formate esters or methanol and catalyst therefor Download PDF

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Publication number
US7208642B2
US7208642B2 US10/030,368 US3036801A US7208642B2 US 7208642 B2 US7208642 B2 US 7208642B2 US 3036801 A US3036801 A US 3036801A US 7208642 B2 US7208642 B2 US 7208642B2
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catalyst
methanol
alkali metal
reaction
type catalyst
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US20030013930A1 (en
Inventor
Kaoru Fujimoto
Noritatsu Tsubaki
Kenichiro Fujimoto
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Nippon Steel Corp
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Nippon Steel Corp
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Assigned to NIPPON STEEL CORPORATION reassignment NIPPON STEEL CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: FUJIMOTO, KAORU, FUJIMOTO, KENICHIRO, TSUBAKI, NORITATSU
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • the present invention relates to a process for producing a formic ester or methanol and a synthesis catalyst therefor. More specifically, the present invention relates to a process for producing a methanol from carbon monoxide and hydrogen using a catalyst having high resistance against decrease in the activity due to water or carbon dioxide and thereby obtaining a product with high efficiency, and also relates to a catalyst therefor.
  • the object of the present invention is to overcome the above-described problems and provide a catalyst and a method, where the catalyst activity is kept even when carbon dioxide, water and the like are included in the starting material gas and/or the reaction system at the synthesis of formic ester or methanol and the formic ester or methanol can be synthesized at low temperatures and low pressures.
  • the present invention is characterized by the followings.
  • a process for producing a formic ester comprising reacting carbon monoxide with an alcohol to produce a formic ester, wherein the reaction is performed in the presence of an alkali metal-type catalyst and/or an alkaline earth metal-type catalyst.
  • a process for producing a methanol comprising reacting carbon monoxide with an alcohol in the presence of an alkali metal-type catalyst and/or an alkaline earth metal-type catalyst to produce a formic ester, wherein a hydrogenolysis catalyst of formic ester and hydrogen are allowed to be present together in the reaction system to hydrogenate the produced formic ester and thereby obtain a methanol.
  • a process for producing a methanol comprising reacting carbon monoxide with an alcohol in the presence of an alkali metal-type catalyst and/or an alkaline earth metal-type catalyst to produce a formic ester, separating the produced formic ester and hydrogenating the separated formic ester by allowing a hydrogenolysis catalyst and hydrogen to be present together, thereby obtaining a methanol.
  • a process for producing a methanol comprising reacting an alcohol in the presence of an alkali metal-type catalyst and/or an alkaline earth metal-type catalyst, and a catalyst that includes Cu simultaneously with Mn and/or Re to obtain a methanol from carbon monoxide and hydrogen.
  • a process for producing a formic ester comprising reacting carbon monoxide with an alcohol, wherein the reaction is performed in the presence of a catalyst containing Cu simultaneously with Mn and/or Re.
  • a catalyst for producing a methanol which is obtained by loading an alkali metal-type catalyst and/or an alkaline earth metal-type catalyst on a solid hydrogenolysis catalyst for formic ester.
  • a catalyst for producing a methanol which is composed of an alkali metal-type catalyst and/or an alkaline earth metal-type catalyst, as well as a catalyst containing Cu simultaneously with Mn and/or Re.
  • a catalyst for producing a formic ester comprising Cu simultaneously with Mn and/or Re.
  • alkali metal-type catalysts include metal compounds and elementary substances, such as lithium, potassium, sodium and cesium.
  • alkaline earth metal-type catalysts include metal compounds and elementary substances, such as calcium, magnesium, barium and strontium.
  • the metal compounds are preferably metal salts or metal oxides, more preferably alkali metal salts such as carbonates, nitrates, phosphates, acetates and formates.
  • alkali metal alkoxides e.g., methoxide, ethoxide
  • Those catalysts can also be used as a catalyst supported on a general support by an ordinary method.
  • the alcohols used for the reaction are an alcohol resultant from bonding of a hydroxyl group to a chained or alicyclic hydrocarbon and in addition, may be a phenol or a substitution product thereof, or a thiol or a substitution product thereof.
  • These alcohols may be primary, secondary or tertiary alcohols, but preferably primary alcohols due to their reaction efficiency. Lower alcohols, such as methyl alcohol or ethyl alcohol, are most commonly used.
  • the reaction may be performed in either the liquid or gas phase but a system where moderate conditions can be selected may be employed. To speak specifically, the temperature, the pressure and the reaction time are selected from 70 to 250° C., 3 to 70 atm and 5 minutes to 10 hours, respectively, however, the conditions are not limited thereto.
  • the alcohol may be sufficient if the amount added thereof is sufficiently large to allow the reaction to proceed, however, the alcohol may also be used as a solvent and in an amount larger than that. In this reaction, organic solvents other than alcohols may be appropriately used in combination.
  • a catalyst containing Cu simultaneously with Mn and/or Re may also be used in the production of a formic ester.
  • the obtained formic ester may be purified by an ordinary method but may also be used as it is in the production of a methanol. That is, a methanol can be produced by hydrogenating the formic ester.
  • a hydrogenolysis catalyst is used and examples of the catalyst which can be used include general hydrogenolysis catalysts containing Cu, Pt, Ni, Co, Ru or Pd. More specifically, copper-type catalysts such as Cu/MnO X , Cu/ReO X (wherein X is a chemically allowable value), Cu/ZnO, Cu/CrO 3 and Raney copper, and nickel-type catalysts are suitably used.
  • the method for preparing the hydrogenolysis catalysts is not particularly limited and an ordinary method may be used, such as impregnation method, precipitation method, sol-gel method, coprecipitation method, ion exchange method, kneading method and drying method.
  • an ordinary method such as impregnation method, precipitation method, sol-gel method, coprecipitation method, ion exchange method, kneading method and drying method.
  • a catalyst having a high loading amount can be prepared and good results can be readily obtained.
  • this hydrogenolysis catalyst and hydrogen are allowed to be present together in the reaction system for producing a formic ester from a carbon monoxide and an alcohol, whereby a methanol can be produced by a so-called one-step process.
  • the hydrogenolysis reaction can be performed fundamentally under the above-described reaction conditions, however, the temperature and the pressure may be appropriately changed.
  • the hydrogen/carbon monoxide ratio is generally selected in the range approximately from 1 to 5.
  • these catalysts may be used as a simple mixture, however, when the alkali metal-type catalyst is supported on the solid hydrogenolysis catalyst, the recovery of the catalysts is advantageously facilitated.
  • an ordinary method employed in the preparation of catalysts may be used.
  • carbon monoxide and hydrogen are used as the starting materials for producing a methanol and the alcohol can be recovered and reused.
  • the catalyst does not lose its activity and a formic ester or a methanol can be produced.
  • a sulfur-type compound and a chlorine-type compound, such as H 2 S and HCl are mingled in the reaction system, the formic ester or a methanol can be similarly produced without any problem.
  • the reaction was performed by the method described in Example 1 except for changing the reaction time to 20 minutes. The same results as in Example 1 were obtained and it was revealed that the reaction reached the equilibrium in 20 minutes.
  • the reaction was performed by the method described in Example 1 except for adding cesium carbonate in place of potassium carbonate.
  • the CO conversion was 3.2%.
  • the reaction was performed by the method described in Example 1 except for adding sodium carbonate in place of potassium carbonate.
  • the CO conversion was 1.36%.
  • the reaction was performed by the method described in Example 1 except for adding lithium carbonate in place of potassium carbonate.
  • the Co conversion was 0.4%.
  • the reaction was performed by the method described in Example 1 except for adding potassium nitrate in place of potassium carbonate.
  • the CO conversion was 1.0%.
  • the reaction was performed by the method described in Example 1 except for adding sodium nitrate in place of potassium carbonate.
  • the CO conversion was 0.9%.
  • the reaction was performed by the method described in Example 1 except for adding potassium phosphate in place of potassium carbonate.
  • the CO conversion was 1.7%.
  • the reaction was performed by the method described in Example 1 except for adding potassium acetate in place of potassium carbonate.
  • the CO conversion was 1.51%.
  • the reaction was performed by the method described in Example 1 except for adding potassium formate in place of potassium carbonate.
  • the CO conversion was 3.44%.
  • the reaction was performed by the method described in Example 1 except for using n-propanol in place of ethanol.
  • the CO conversion was 3.4% (n-propyl formate).
  • the reaction was performed by the method described in Example 1 except for using n-butanol in place of ethanol.
  • the CO conversion was 3.4% (n-butyl formate).
  • the reaction was performed by the method described in Example 1 except for using i-propanol in place of ethanol.
  • the CO conversion was 1.1% (i-propyl formate).
  • the reaction was performed by the method described in Example 1 except for using i-butanol in place of ethanol.
  • the CO conversion was 1.8% (i-butyl formate).
  • the reaction was performed by the method described in Example 1 except for using t-butanol in place of ethanol.
  • the CO conversion was 0.7% (t-butyl formate).
  • the reaction was performed by the method described in Example 1 except for further adding 0.2 g of a copper/zinc coprecipitated catalyst as the hydrogenolysis catalyst. As a result, methanol was obtained with the CO conversion of 2.9% and the methanol yield of 0.3%.
  • the reaction was performed by the method described in Example 19 except for further adding 4.0 g of a copper/zinc coprecipitated catalyst as the hydrogenolysis catalyst. As a result, methanol was obtained with the CO conversion of 25% and the methanol yield of 1.2%.
  • the reaction was performed by the method described in Example 19 except for further adding 4.0 g of a copper/manganese coprecipitated catalyst as the hydrogenolysis catalyst. As a result, methanol was obtained with the CO conversion of 90% and the methanol yield of 27%.
  • the reaction was performed by the method described in Example 19 except for further adding 2.0 g of a copper/manganese coprecipitated catalyst as the hydrogenolysis catalyst. As a result, methanol was obtained with the CO conversion of 79% and the methanol yield of 27%.
  • the reaction was performed by the method described in Example 19 except for further adding 1.0 g of a copper/manganese coprecipitated catalyst as the hydrogenolysis catalyst. As a result, methanol was obtained with the CO conversion of 33% and the methanol yield of 1.1%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)
US10/030,368 2000-02-25 2001-02-23 Process for preparation of formate esters or methanol and catalyst therefor Expired - Fee Related US7208642B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US10/793,439 US7081547B2 (en) 2000-02-25 2004-03-04 Process for producing formic ester or methanol and synthesis catalyst therefor

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2000-500046 2000-02-05
JP2000050046 2000-02-25
PCT/JP2001/001386 WO2001062701A1 (fr) 2000-02-25 2001-02-23 Procede de preparation d'esters de formate ou de methanol et catalyseur destine a cet effet

Related Parent Applications (1)

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PCT/JP2001/001386 A-371-Of-International WO2001062701A1 (fr) 2000-02-25 2001-02-23 Procede de preparation d'esters de formate ou de methanol et catalyseur destine a cet effet

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US (2) US7208642B2 (zh)
EP (1) EP1180511B1 (zh)
JP (1) JP5067996B2 (zh)
KR (2) KR100567039B1 (zh)
CN (2) CN1258516C (zh)
CA (1) CA2370793C (zh)
DE (1) DE60139842D1 (zh)
DK (1) DK1180511T3 (zh)
RU (1) RU2231521C2 (zh)
WO (1) WO2001062701A1 (zh)

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WO2001062701A1 (fr) 2001-08-30
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